U.S. patent application number 16/771945 was filed with the patent office on 2021-03-11 for zirconium-based cluster as an antiperspirant and deodorant active.
This patent application is currently assigned to Colgate-Palmolive Company. The applicant listed for this patent is Colgate-Palmolive Company. Invention is credited to Viktor DUBOVOY, Long PAN, Ravi SUBRAMANYAM.
Application Number | 20210069074 16/771945 |
Document ID | / |
Family ID | 1000005241370 |
Filed Date | 2021-03-11 |
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United States Patent
Application |
20210069074 |
Kind Code |
A1 |
DUBOVOY; Viktor ; et
al. |
March 11, 2021 |
Zirconium-Based Cluster as an Antiperspirant and Deodorant
Active
Abstract
Described herein are zirconium oxychloride clusters comprising
zirconium oxychloride and a basic amino acid. Personal care
compositions comprising the same, and methods of making and using
the same are also described.
Inventors: |
DUBOVOY; Viktor; (Cresskill,
NJ) ; PAN; Long; (Somerset, NJ) ; SUBRAMANYAM;
Ravi; (Belle Mead, NJ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Colgate-Palmolive Company |
New York |
NY |
US |
|
|
Assignee: |
Colgate-Palmolive Company
New York
NY
|
Family ID: |
1000005241370 |
Appl. No.: |
16/771945 |
Filed: |
December 10, 2018 |
PCT Filed: |
December 10, 2018 |
PCT NO: |
PCT/US2018/064756 |
371 Date: |
June 11, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62598504 |
Dec 14, 2017 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A61Q 5/12 20130101; A61Q
15/00 20130101; A61Q 19/10 20130101; A61K 8/44 20130101; A61Q 5/02
20130101; A61K 8/0275 20130101; A61K 2800/805 20130101; A61K 8/28
20130101; A61K 8/26 20130101; A61K 2800/30 20130101 |
International
Class: |
A61K 8/28 20060101
A61K008/28; A61K 8/44 20060101 A61K008/44; A61K 8/02 20060101
A61K008/02; A61K 8/26 20060101 A61K008/26; A61Q 19/10 20060101
A61Q019/10; A61Q 15/00 20060101 A61Q015/00; A61Q 5/12 20060101
A61Q005/12; A61Q 5/02 20060101 A61Q005/02 |
Claims
1. A zirconium oxychloride cluster comprising: a. zirconium
oxychloride; and b. a basic amino acid; wherein the cluster has a
radius of gyration of from 0.5 nm to 50 nm.
2. The cluster of claim 1, wherein the zirconium oxychloride
cluster has a radius of gyration of from 0.5 nm to 20 nm, from 0.5
nm to 10 nm, from 0.7 nm to 10 nm, from 0.8 nm to 10 nm, from 1 nm
to 10 nm, from 0.5 nm to 7 nm, from 0.6 nm to 6 nm, from 0.7 nm to
5 nm, from 0.8 nm to 3 nm, from 0.8 nm to 2.5 nm, or from 1 nm to 2
nm.
3. The cluster of claim 1, wherein the zirconium oxychloride
cluster is stable at pH 2-6, 3-5, 3-4, 3.5-4.5 or 4-4.5.
4. The cluster of claim 1, wherein the zirconium oxychloride
cluster exhibits a SEC chromatogram having a high peak at 6-8
minutes; wherein the SEC chromatogram is obtained under conditions
wherein SEC chromatography is carried out using a 10 .mu.m
diol-bonded gel filtration column with 20 min run time and 1 mL/min
flow rate and the mobile phase of the SEC chromatography consists
of deionized water acidified with 1.01% w/w HNO.sub.3 to pH
2.3.
5. The cluster claim 1, wherein the basic amino acid comprises
arginine.
6. The cluster of claim 1 prepared by a process comprising the
steps of: (a) combining a basic amino acid and zirconium
oxychloride in an aqueous solution; (b) incubating the solution at
a temperature higher than 40.degree. C.; and (c) cooling the
solution; wherein the molar ratio of the basic amino acid to
zirconium oxychloride in step (a) is less than 1.5.
7. The cluster of claim 6, wherein the molar ratio of the basic
amino acid to zirconium oxychloride in step (a) is from 0.5 to 1.5,
from 0.7 to 1.3, from 0.8 to 1.2, from 0.9 to 1.1, or about 1.
8. The cluster of claim 6, wherein the basic amino acid in step (a)
is arginine.
9. The cluster of claim 8, wherein the arginine is L-arginine.
10. The cluster of claim 6, wherein the process further comprises
the step of purifying the zirconium oxychloride cluster from the
cooled solution.
11. The cluster of claim 10, wherein the zirconium oxychloride
cluster is purified by gel permeation chromatography (GPC).
12. The cluster of claim 11, wherein the GPC column comprises
polyacrylamide beads having a wet bead size of less than 45 .mu.m
and a 100-1,800 MW fractionation range.
13. The cluster of claim 12, wherein the purification comprises
loading the cooled solution on the GPC column using a HPLC pump at
0.2 mL/min; and the mobile phase of the GPC chromatography is
deionized water.
14. The cluster of claim 13, wherein GPC fraction is collected in
the 1160-1300 minute interval and wherein the 1160-1300 minute
interval fraction contains the purified zirconium cluster.
15. A personal care composition comprising a zirconium oxychloride
cluster according to claim 1.
16. The personal care composition of claim 15, wherein the personal
care composition comprises an aluminum containing antiperspirant
active.
17. The personal care composition of claim 15, wherein the personal
care composition does not contain any aluminum containing
antiperspirant active.
18. The personal care composition of claim 15, wherein the personal
care composition is selected from an antiperspirant, a deodorant, a
body wash, a shower gel, a bar soap, a shampoo, a hair conditioner,
and a cosmetic.
19. A method of preparing a zirconium oxychloride cluster having a
radius of gyration of from 0.5 nm to 50 nm, comprising the steps
of: (a) combining a basic amino acid and zirconium oxychloride in
an aqueous solution; (b) incubating the solution at a temperature
higher than 40.degree. C.; and (c) cooling the solution; wherein
the molar ratio of the basic amino acid to zirconium oxychloride in
step (a) is less than 1.5.
20. The method of claim 19, wherein the molar ratio of the basic
amino acid to zirconium oxychloride in step (a) is from 0.5 to 1.5,
from 0.7 to 1.3, from 0.8 to 1.2, from 0.9 to 1.1, or about 1.
21. (canceled)
22. (canceled)
23. (canceled)
24. (canceled)
25. (canceled)
Description
BACKGROUND
[0001] Antiperspirants are personal hygiene products designed to
control sweating and body odor. Antiperspirants contain ingredients
that control sweat and body odor safely and effectively. When an
antiperspirant is applied to the skin surface, its antiperspirant
ingredients, e.g., aluminum salts, dissolve in the sweat or
moisture on the skin. The dissolved substance forms a gel, which
creates a small temporary plug near the top of the sweat gland,
significantly reducing the amount of sweat that is secreted to the
skin surface. Antiperspirant actives may also flocculate proteins
present in the sweat to form a precipitate which blocks the sweat
glands. Although antiperspirants reduce sweating, they do not
impact on the natural ability of the body to control its
temperature.
[0002] It has been known that zirconium salts exhibit effective
antiperspirant properties such zirconium compounds include acidic
zirconium salts such as zirconium oxychloride or zirconyl chloride,
zirconium hydroxychloride, and other halide and sulfate substitutes
of the salts. Due to the large charge to size ratio of Zr.sup.4+,
zirconium compounds provide superior sweat reduction efficacy but
has a high skin irritation potential. According to FDA
antiperspirant over-the-counter monograph, zirconium compounds may
be added into polymerized aluminum chloride systems to produce
aluminum zirconium chlorohydrates, optionally comprising glycine.
The zirconium salts are extremely acidic and irritating to the
skin. For example, a solution of zirconium oxychloride which is
effective as an antiperspirant has a pH of about 0.8. Thus,
zirconium oxychloride alone cannot be used in a topical product due
to its extremely low pH value. Moreover, decreasing the acidity of
zirconium compounds using weak acids, e.g., organic acids, tends to
decrease their antiperspirant efficacy.
[0003] There is a need for partially neutralized zirconium
compounds that overcome the undesirable effects of highly acidic
zirconium compounds and at the same time exhibit desirable
properties as antiperspirant/deodorant actives or water treatment
agents.
BRIEF SUMMARY
[0004] The present invention provides zirconium oxychloride
clusters comprising zirconium oxychloride and a basic amino acid
e.g., arginine, having a radius of gyration of from 0.5 nm to 50
nm, e.g., from 0.5 nm to 20 nm, from 0.5 nm to 10 nm, from 0.7 nm
to 10 nm, from 0.8 nm to 10 nm, from 1 nm to 10 nm, from 0.5 nm to
7 nm, from 0.6 nm to 6 nm, from 0.7 nm to 5 nm, from 0.8 nm to 3
nm, from 0.8 nm to 2.5 nm, or from 1 nm to 2 nm. In some
embodiments, the zirconium oxychloride cluster is stable at pH 2-6,
3-5, 3-4, 3.5-4.5, or 4-4.5. In some embodiments, the zirconium
oxychloride cluster exhibits a SEC chromatogram having a high peak
at 6-8 minutes, 6.5-7.5 minutes, 6.5-7 minutes, or about 6.75
minutes, wherein the SEC chromatogram is obtained under conditions
wherein SEC chromatography is carried out using a 10 .mu.m
diol-bonded gel filtration column with 20 min run time and 1 mL/min
flow rate and the mobile phase of the SEC chromatography consists
of deionized water acidified with 1.01% w/w HNO.sub.3 to pH 2.3. In
some embodiments, the zirconium oxychloride cluster is prepared by
a process comprising the steps of: (a) combining a basic amino
acid, e.g., arginine, and zirconium oxychloride in aqueous
solution; (b) incubating the solution at a temperature higher than
40.degree. C., e.g., from 40.degree. C. to 60.degree. C., from
45.degree. C. to 55.degree. C., or about 50.degree. C.; and (c)
cooling the solution, wherein the molar ratio of the basic amino
acid to zirconium oxychloride is less than 1.5, e.g., from 0.5 to
1.5, from 0.7 to 1.3, from 0.8 to 1.2, from 0.9 to 1.1, or about 1.
In some embodiments, the zirconium oxychloride cluster may be
amorphous.
[0005] The present invention also provides personal care products,
e.g., antiperspirants, comprising the zirconium oxychloride cluster
of the invention. In some embodiments, the personal care product
further comprises an aluminum containing antiperspirant active. In
some embodiments, the personal care product does not contain any
aluminum containing antiperspirant active.
[0006] The present invention also provides methods of preparing the
zirconium oxychloride cluster of the invention, comprising the
steps of: (a) combining a basic amino acid, e.g., arginine, and
zirconium oxychloride in an aqueous solution; (b) incubating the
solution at a temperature higher than 40.degree. C., e.g., from
40.degree. C. to 60.degree. C., from 45.degree. C. to 55.degree.
C., or about 50.degree. C.; and (c) cooling the solution, wherein
the molar ratio of the basic amino acid to zirconium oxychloride in
step (a) is less than 1.5, e.g., from 0.5 to 1.5, from 0.7 to 1.3,
from 0.8 to 1.2, from 0.9 to 1.1, or about 1.
[0007] The present invention also provides use of the zirconium
oxychloride cluster of the invention as an antiperspirant or
deodorant active or water treatment agent.
[0008] Further areas of applicability of the present disclosure
will become apparent from the detailed description provided
hereinafter. It should be understood that the detailed description
and specific examples, while indicating the preferred embodiment of
the disclosure, are intended for purposes of illustration only and
are not intended to limit the scope of the disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] The present invention will become more fully understood from
the detailed description and the accompanying drawings.
[0010] FIG. 1 illustrates a SEC chromatogram of a solution (Arg/Zr
1) in Example 1.
[0011] FIG. 2 illustrates a SEC chromatogram of the GPC fraction
1160-1300 min in Example 2.
DETAILED DESCRIPTION
[0012] The following description of the preferred embodiment(s) is
merely exemplary in nature and is in no way intended to limit the
invention, its application, or uses.
[0013] As used throughout, ranges are used as shorthand for
describing each and every value that is within the range. Any value
within the range can be selected as the terminus of the range. In
addition, all references cited herein are hereby incorporated by
referenced in their entireties. In the event of a conflict in a
definition in the present disclosure and that of a cited reference,
the present disclosure controls.
[0014] Unless otherwise specified, all percentages and amounts
expressed herein and elsewhere in the specification should be
understood to refer to percentages by weight. The amounts given are
based on the active weight of the material.
[0015] The present invention provides a zirconium oxychloride
cluster (Cluster 1.0) comprising zirconium oxychloride and a basic
amino acid e.g., arginine, having a radius of gyration of from 0.5
nm to 50 nm, e.g., from 0.5 nm to 20 nm, from 0.5 nm to 10 nm, from
0.7 nm to 10 nm, from 0.8 nm to 10 nm, from 1 nm to 10 nm, from 0.5
nm to 7 nm, from 0.6 nm to 6 nm, from 0.7 nm to 5 nm, from 0.8 nm
to 3 nm, from 0.8 nm to 2.5 nm, or from 1 nm to 2 nm. [0016] 1.1.
Cluster 1.0, wherein the radius of gyration of the zirconium
oxychloride cluster is measured by small angle X-ray scattering
(SAXS). [0017] 1.2. Cluster 1.0 or 1.1, wherein the zirconium
oxychloride cluster is amorphous. [0018] 1.3. Any of the preceding
clusters, wherein the zirconium oxychloride cluster is stable at pH
2-6, 3-5, 3-4, 3.5-4.5, or 4-4.5. [0019] 1.4. Any of the preceding
clusters, wherein the zirconium oxychloride cluster exhibits a SEC
chromatogram having a high peak at 6-8 minutes, 6.5-7.5 minutes,
6.5-7 minutes, or about 6.75 minutes; and wherein the SEC
chromatogram is obtained under conditions wherein SEC
chromatography is carried out using a 10 .mu.m diol-bonded gel
filtration column with 20 min run time and 1 mL/min flow rate and
the mobile phase of the SEC chromatography consists of deionized
water acidified with 1.01% w/w HNO.sub.3 to pH 2.3. [0020] 1.5. Any
of the preceding clusters, wherein the basic amino acid is present
in an amount of less than 5%, less than 1%, less than 0.1%, less
than 0.01%, less than 0.001%, or less than 0.0001%, by weight of
the cluster. [0021] 1.6. Any of the preceding clusters, wherein the
basic amino acid comprises arginine. [0022] 1.7. Cluster 1.6,
wherein the basic amino acid comprises L-arginine. [0023] 1.8. Any
of the preceding cluster prepared by a process comprising the steps
of: [0024] (a) combining a basic amino acid and zirconium
oxychloride in an aqueous solution; [0025] (b) incubating the
solution at a temperature higher than 40.degree. C., e.g., from
40.degree. C. to 60.degree. C., from 45.degree. C. to 55.degree.
C., or about 50.degree. C.; and [0026] (c) cooling the solution;
[0027] wherein the molar ratio of the basic amino acid to zirconium
oxychloride in step (a) is less than 1.5. [0028] 1.9. Cluster 1.8,
wherein the process further comprises the step of purifying the
zirconium oxychloride cluster from the cooled solution. [0029]
1.10. Cluster 1.9, wherein the zirconium oxychloride cluster is
purified by gel permeation chromatography (GPC). [0030] 1.11.
Cluster 1.10, wherein the GPC column comprises polyacrylamide beads
having a wet bead size of less than 45 .mu.m and a 100-1,800 MW
fractionation range. [0031] 1.12. Cluster 1.11, wherein the
purification comprises loading the cooled solution on the GPC
column using a HPLC pump at 0.2 mL/min; and the mobile phase of the
GPC chromatography is deionized water. [0032] 1.13. Cluster 1.12,
wherein GPC fraction is collected in the 1160-1300 minute interval
and wherein the 1160-1300 minute interval fraction contains the
purified zirconium oxychloride cluster. [0033] 1.14. Any of
Clusters 1.10-1.13, wherein the process further comprises the step
of freeze drying the GPC fraction. [0034] 1.15. Any of Clusters
1.8-1.14, wherein the molar ratio of the basic amino acid to
zirconium oxychloride in step (a) is from 0.5 to 1.5, from 0.7 to
1.3, from 0.8 to 1.2, from 0.9 to 1.1, or about 1. [0035] 1.16. Any
of Clusters 1.8-1.15, wherein the basic amino acid in step (a) is
arginine. [0036] 1.17. Cluster 1.16, wherein the basic amino acid
in step (a) is L-arginine. [0037] 1.18. Any of Clusters 1.8-1.17,
wherein the aqueous solution in step (a) is water.
[0038] The present invention also provides a method (Method 2.0)
for the preparation of a zirconium oxychloride cluster having a
radius of gyration of from 0.5 nm to 50 nm, e.g., from 0.5 nm to 20
nm, from 0.5 nm to 10 nm, from 0.7 nm to 10 nm, from 0.8 nm to 10
nm, from 1 nm to 10 nm, from 0.5 nm to 7 nm, from 0.6 nm to 6 nm,
from 0.7 nm to 5 nm, from 0.8 nm to 3 nm, from 0.8 nm to 2.5 nm, or
from 1 nm to 2 nm, comprising the steps of: [0039] (a) combining a
basic amino acid and zirconium oxychloride in an aqueous solution;
[0040] (b) incubating the solution at a temperature higher than
40.degree. C., e.g., from 40.degree. C. to 60.degree. C., from
45.degree. C. to 55.degree. C., or about 50.degree. C.; and [0041]
(c) cooling the solution; wherein the molar ratio of the basic
amino acid to zirconium oxychloride in step (a) is less than 1.5.
[0042] 2.1. Method 2.0, wherein the method further comprises the
step of purifying the zirconium oxychloride cluster from the cooled
solution. [0043] 2.2. Method 2.1, wherein the zirconium oxychloride
cluster is purified by gel permeation chromatography (GPC). [0044]
2.3. Method 2.2, wherein the GPC column comprises polyacrylamide
beads having a wet bead size of less than 45 .mu.m and a 100-1,800
MW fractionation range. [0045] 2.4. Method 2.3, wherein the
purification comprises loading the cooled solution on the GPC
column using a HPLC pump at 0.2 mL/min; and the mobile phase of the
GPC chromatography is deionized water. [0046] 2.5. Method 2.4,
wherein GPC fraction is collected in the 1160-1300 minute interval,
and wherein the 1160-1300 minute interval fraction contains the
purified zirconium oxychloride cluster. [0047] 2.6. Any of Methods
2.2-2.5, wherein the method further comprises the step of freeze
drying the GPC fraction. [0048] 2.7. Any of the preceding methods,
wherein the molar ratio of the basic amino acid to zirconium
oxychloride in step (a) is from 0.5 to 1.5, from 0.7 to 1.3, from
0.8 to 1.2, or about 1. [0049] 2.8. Any of the preceding methods,
wherein the basic amino acid in step (a) is arginine. [0050] 2.9.
Any of the preceding methods, wherein the basic amino acid in step
(a) is L-arginine. [0051] 2.10. Any of the preceding methods,
wherein the aqueous solution in step (a) is water. [0052] 2.11. Any
of the preceding methods, wherein the radius of gyration of the
zirconium oxychloride cluster is measured by small angle X-ray
scattering (SAXS). [0053] 2.12. Any of the preceding methods,
wherein the zirconium oxychloride cluster is amorphous. [0054]
2.13. Any of the preceding methods, wherein the zirconium
oxychloride cluster is stable at pH 2-6, 3-5, 3-4, 3.5-4.5 or
4-4.5. [0055] 2.14. Any of the preceding methods, wherein the
zirconium oxychloride cluster exhibits a SEC chromatogram having a
high peak at 6-8 minutes, 6.5-7.5 minutes, 6.5-7 minutes, or about
6.75 minutes; and wherein the SEC chromatogram is obtained under
conditions wherein SEC chromatography is carried out using a 10
.mu.m diol-bonded gel filtration column with 20 min run time and 1
mL/min flow rate and the mobile phase of the SEC chromatography
consists of deionized water acidified with 1.01% w/w HNO.sub.3 to
pH 2.3. [0056] 2.15. Any of the preceding methods, wherein the
zirconium oxychloride cluster comprises the basic amino acid.
[0057] The term "zirconium oxychloride cluster" herein refers to
any zirconium-based cluster comprising zirconium, chloride, oxygen
and hydrogen atoms. In some embodiments, the zirconium oxychloride
cluster comprises zirconium oxychloride and a basic amino acid. In
some embodiments, the zirconium oxychloride cluster may contain a
small amount of a basic amino acid. For example, the zirconium
oxychloride cluster may contain a basic amino acid in an amount of
less than 5%, less than 1%, less than 0.1%, less than 0.01%, less
than 0.001%, or less than 0.0001%, by weight of the cluster. The
basic amino acid that may be contained in the zirconium oxychloride
cluster include, but are not limited to, arginine, lysine,
citrullene, ornithine, creatine, histidine, diaminobutanoic acid,
diaminopropionic acid, or combinations thereof. In some
embodiments, the basic amino acids are selected from arginine,
lysine, citrullene, and ornithine. In some embodiments, the basic
amino acid comprises arginine, for example, L-arginine.
[0058] The zirconium oxychloride cluster of the present invention
has a radius of gyration of from 0.5 nm to 50 nm, e.g., from 0.5 nm
to 20 nm, from 0.5 nm to 10 nm, from 0.7 nm to 10 nm, from 0.8 nm
to 10 nm, from 1 nm to 10 nm, from 0.5 nm to 7 nm, from 0.6 nm to 6
nm, from 0.7 nm to 5 nm, from 0.8 nm to 3 nm, from 0.8 nm to 2.5
nm, or from 1 nm to 2 nm. Radius of gyration (Rg) may be determined
by well-known techniques in the art, e.g., small angle X-ray
scattering (SAXS) in which X-ray scattering when travelling through
the material is measured at small angles. Radius of gyration (Rg)
can be calculated from the SAXS data using well-known data
processing techniques in the art, e.g., Guinier plot analysis. In
some embodiments, radius of gyration (Rg) of the zirconium
oxychloride cluster is determined by Small angle X-ray scattering
(SAXS) using Guinier plot analysis.
[0059] In some embodiments, the zirconium oxychloride cluster of
the present invention exhibits a SEC chromatogram having a high
peak at 6-8 minutes, 6.5-7.5 minutes, 6.5-7 minutes, or about 6.75
minutes, wherein the SEC chromatogram is obtained under conditions
wherein SEC chromatography is carried out using a 10 .mu.m
diol-bonded gel filtration column, e.g., PAK 125 column by Waters
(Milford, Mass.), with 20 min run time and mL/min flow rate and the
mobile phase of the SEC chromatography consists of deionized water
acidified with 1.01% w/w HNO.sub.3 to pH 2.3.
[0060] Size exclusion chromatography (SEC) is a chromatographic
method in which molecules in solution are separated by their size,
and in some cases molecular weight. SEC provides information on the
size of antiperspirant salts in aqueous solutions. For
antiperspirant salts including aluminum chlorohydrate,
aluminum/zirconium chlorohydrate, and complexes thereof,
distinctive peaks have been identified, corresponding to different
size populations of the polymer complexes in solution, appearing in
a chromatogram as peaks 1, 2, 3, 4 and a peak known as "5,6"
(WO2009/075678 and WO2009/076591). Based on the SEC chromatogram,
it is predicted that the zirconium oxychloride cluster of the
invention has a particle size on the order of nanometer. A peak in
this region of retention time is commonly present in various
non-activated antiperspirant active salts, but seldom observed in
aluminum-free zirconium compounds. In this disclosure, the
zirconium oxychloride cluster of the invention exhibiting a SEC
chromatogram having a high peak at 6-8 minutes, e.g., about 6.75
minutes is also referred to as "Zr peak 1". The SEC technique is
explained fully in WO 2013/158077 and U.S. 2015/0132242, each of
which is incorporated by reference herein in its entirety for all
purposes.
[0061] In some embodiments, the zirconium oxychloride cluster of
the present invention is amorphous.
[0062] In some embodiments, the zirconium oxychloride cluster of
the invention is stable at pH 2-6, 3-5, 3-4, 3.5-4.5 or 4-4.5, in
solution, e.g., in aqueous solution. In this disclosure, the
zirconium oxychloride cluster is stable means that the cluster does
not form a gel or precipitate.
[0063] In some embodiments, the zirconium oxychloride cluster may
be prepared by a process comprising the steps of: (a) combining a
basic amino acid, e.g., arginine, and zirconium oxychloride
(ZrOCl.sub.2.8H.sub.2O, MW 322.25) in an aqueous solution; (b)
incubating the solution at a temperature higher than 40.degree. C.
e.g., from 40.degree. C. to 60.degree. C., from 45.degree. C. to
55.degree. C., or about 50.degree. C.; and (c) cooling the
solution, wherein the molar ratio of the basic amino acid to
zirconium oxychloride is less than 1.5. The solution may be
incubated at a temperature higher than 40.degree. C., e.g., from
40.degree. C. to 60.degree. C., from 45.degree. C. to 55.degree.
C., or about 50.degree. C. for more than 1 hour, e.g., more than 6
hour, more than 12 hour, more than 1 day, from 1 hour to 2 day,
from 6 hour to 2 day, from 12 hour to 2 day, or about 1 day. The
term "zirconium oxychloride" herein refers to zirconium oxychloride
octahydrate (ZrOCl.sub.2.8H.sub.2O, MW 322.25). In the process, low
molar ratio of the basic amino acid to zirconium oxychloride in
step (a) is critical to obtain stable zirconium oxychloride
clusters. When the molar ratio of the basic amino acid to zirconium
oxychloride is high, e.g., more than 2, solid gel forms during the
process. However, when the molar ratio of the basic amino acid to
zirconium oxychloride is low, e.g., less than 1.5, from 0.5 to 1.5,
from 0.8 to 1.2, or about 1, the produced zirconium oxychloride
clusters are stable in terms of gelation and flocculation. In some
embodiments, the molar ratio of the basic amino acid to zirconium
oxychloride in step (a) is from 0.5 to 1.5, from 0.7 to 1.3, from
0.8 to 1.2, or about 1. In some embodiments, the aqueous solution
in step (a) is water.
[0064] In some embodiments, the basic amino acids which can be used
in the process of preparing the zirconium oxychloride cluster of
the invention include not only naturally occurring basic amino
acids, such as arginine, lysine, and histidine, but also any basic
amino acids having a carboxyl group and an amino group in the
molecule. Accordingly, basic amino acids include, but are not
limited to, arginine, lysine, citrullene, ornithine, creatine,
histidine, diaminobutanoic acid, diaminopropionic acid, or
combinations thereof. In some embodiments, the basic amino acids
are selected from arginine, lysine, citrullene, and ornithine. In
some embodiments, the basic amino acid is arginine, for example,
L-arginine.
[0065] In some embodiments, the prepared zirconium oxychloride
cluster may be further purified. For example, zirconium oxychloride
cluster may be purified by gel permeation chromatography (GPC). Gel
permeation chromatography (GPC) is a type of size exclusion
chromatography (SEC) that separates molecules on the base of size.
In some embodiments, the purification comprises loading the
solution containing zirconium oxychloride clusters on the GPC
column comprising polyacrylamide beads having a wet bead size of
less than 45 .mu.m and a 100-1,800 MW fractionation range, e.g.,
Bio-Rad P2 gel with 5 .mu.m particle size, using a HPLC pump at 0.2
mL/min; and the mobile phase of the GPC chromatography is deionized
water. GPC fraction is collected in the 1160-1300 minute interval
and the 1160-1300 minute interval fraction contains the purified
zirconium cluster. In some embodiments, the GPC fraction may be
freeze dried to obtain purified powder.
[0066] Although zirconium oxychloride exhibits effective
antiperspirant properties, zirconium oxychloride alone cannot be
used in a topical product due to its extremely low pH value (less
than pH 2). It has been found that the zirconium oxychloride
cluster of the present invention is stable at higher pH. Thus, the
zirconium oxychloride cluster can overcome the undesirable effects
of highly acidic zirconium compounds. Moreover, it has been found
that the zirconium oxychloride cluster of the invention forms a
precipitate in presence of proteins such as bovine serum albumin
(BSA), suggesting that the zirconium oxychloride cluster can
flocculate proteins present in the sweat to enhance the formation
of plugs in the sweat ducts. Thus, the zirconium oxychloride
cluster of the invention can be used as an antiperspirant and
deodorant active.
[0067] The present invention also provides personal care
compositions, e.g., antiperspirants, comprising a zirconium
oxychloride cluster according to any of Clusters 1.0-1.18. The
personal care composition may be any composition in which it is
desired to include an antiperspirant and deodorant active for
application to the skin. Examples of such compositions include, but
are not limited to, antiperspirants, deodorants, body washes,
shower gels, bar soaps, shampoo, hair conditioners, cosmetics,
etc.
[0068] In some embodiments, the zirconium oxychloride cluster used
in the personal care composition may be prepared by a method
according to any of Methods 2.0-2.15. The zirconium oxychloride
cluster used in the personal care composition may be a purified or
unpurified form.
[0069] The personal care composition contains a carrier. For
antiperspirant/deodorant compositions, the carrier can be any
carrier that is used for antiperspirants/deodorants. The carrier
can be in the form of a stick, a gel, a roll-on, or an aerosol. For
stick formulations, the carrier may include oils and/or silicones
and gelling agents.
[0070] The antiperspirant compositions can be formulated into
topical antiperspirant and/or deodorant formulations suitable for
application to skin, illustratively a stick, a gel, a cream, a
roll-on, a soft solid, a powder, a liquid, an emulsion, a
suspension, a dispersion or a spray. The composition can comprise a
single phase or can be a multi-phase system, for example a system
comprising a polar phase and an oil phase, optionally in the form
of a stable emulsion. The composition can be liquid, semi-solid or
solid. The antiperspirant and/or deodorant formulation can be
provided in any suitable container such as an aerosol can, tube or
container with a porous cap, roll-on container, bottle, container
with an open end, etc.
[0071] Optional ingredients that can be included in an
antiperspirant and/or deodorant formulation include solvents;
water-soluble alcohols such as C.sub.2-8 alcohols including
ethanol; glycols including propylene glycol, dipropylene glycol,
tripropylene glycol and mixtures thereof; glycerides including
mono-, di- and triglycerides; medium to long chain organic acids,
alcohols and esters; surfactants including emulsifying and
dispersing agents; amino acids including glycine; structurants
including thickeners and gelling agents, for example polymers,
silicates and silicon dioxide; emollients; fragrances; and
colorants including dyes and pigments. If desired, an
antiperspirant and/or deodorant agent additional to the zirconium
oxychloride cluster can be included, for example an odor reducing
agent such as a sulfur precipitating agent, e.g., copper gluconate,
zinc gluconate, zinc citrate, etc.
[0072] In some embodiments, the personal care composition may
further comprise additional antiperspirant actives. The additional
active antiperspirant ingredient may be selected from aluminum
salts, zirconium salts and zinc salts. In some embodiment, the
personal care composition may comprise an aluminum containing
antiperspirant active. Any of the known aluminum containing
antiperspirant active materials can be utilized in the composition.
Aluminum containing antiperspirant actives include, but are not
limited to, aluminum chlorohydrate, aluminum chloride, aluminum
chlorohydrex polyethylene glycol, aluminum chlorohydrex propylene
glycol, aluminum dichlorohydrate, aluminum dichlorohydrex
polyethylene glycol, aluminum dichlorohydrex propylene glycol,
aluminum sesquichlorohydrate, aluminum, sesquichlorohydrate
polyethylene glycol, aluminum sesquichlorohydrate propylene
glycol.
[0073] In some embodiments, the personal care composition does not
contain any other antiperspirant active. In some embodiment, the
personal care composition does not contain any aluminum containing
antiperspirant active.
[0074] In some embodiments, the personal care composition may
include any known deodorant active. Examples of deodorant actives
include, but are not limited to, antimicrobial actives, alcohols,
2,4,4'-trichloro-2'-hydroxy diphenyl ether (Triclosan),
benzethonium chloride, polyhexamethylene biguanides,
triethylcitrate, 2-amino-2-methyl-1-propanol (AMP),
cetyl-trimethylammomium bromide, cetyl pyridinium chloride,
farnesol (3,7, 11-trimethyl-2,6,10-dodecatrien-1-ol),
N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)urea (Triclocarban),
silver halides, octoxyglycerin (Sensiva.TM. SC 50) and various zinc
salts (for example, zinc ricinoleate), bactericides, and/or
bacteriostats. The deodorant active can be included in the
composition in an amount of 0-5%, or 0.01-1% by weight, of the
total weight of the composition. Triclosan can be included in an
amount of 0.05% to 0.5% by weight, of the total weight of the
composition.
[0075] In some embodiments, gelling agents may be included in the
personal care composition. Examples of gelling agents include, but
are not limited to, waxes, esters of fatty acid and fatty alcohol,
triglycerides, partially or fully hydrogenated soybean oil,
partially or fully hydrogenated castor oil, other partial or fully
hydrogenated plant oils, stearyl alcohol, or other cosmetically
acceptable materials, which are solid or semi-solid at room
temperature and provide a consistency suitable for application to
the skin.
[0076] In some embodiments, fragrance may be included in the
personal care composition. Any fragrance suitable for personal care
use may be incorporated into the personal care composition of the
present invention. Fragrances tend to be relatively volatile aroma
compounds which are capable of entering the gas phase at skin
surface temperature.
[0077] The personal care compositions of the present invention may
be manufactured using methods known in the art. Typically, the
ingredients are combined and optionally heated where components
need to be melted. The components are mixed. Desirably, volatile
materials such as fragrant materials are incorporated in the
composition in the latter stages of a mixing cycle in order to
avoid volatilization thereof. After mixing, the composition may be
poured directly into the dispensers and the container capped to
preserve the product until use.
[0078] The present invention also provides use of the zirconium
oxychloride cluster as described herein as an antiperspirant or
deodorant active or water treatment agent.
EXAMPLES
Example 1: Preparation of Zirconium Oxychloride Clusters
[0079] Samples were prepared according to Table 1. Water was added
to zirconium oxychloride (ZrOCl.sub.2.8H.sub.2O, MW 322.25) in a
glass jar to yield a clear solution containing 1% zirconium
oxychloride. Under stirring, L-arginine was slowly added to prevent
clumping of arginine as well as large fluctuations in localized pH
values. The molar ratio of arginine to zirconium oxychloride was
0.5:1, 1:1, 2:1, 3:1, and 4:1, as shown in Table 1. The solutions
were incubated for 1 day at 50.degree. C. Then the solutions were
cooled to room temperature. Solid gel was formed in samples with
the molar ratio of arginine to zirconium oxychloride of 2-4.
However, at the molar ratio of arginine to zirconium oxychloride to
0, 0.5 and 1, the samples were stable in terms of gelation and
flocculation with pH of 1.39, 1.73, and 2.59, respectively.
TABLE-US-00001 TABLE 1 1% zirconium oxychloride with varied
arginine Calculated Experimental Arg/Zr Zr Arg Total Arg/Zr Zr Arg
Total Sample mol g g g mol g g g pH Zr 0 0.3533 0 10 0 0.3533 0
9.9928 1.39 clear Arg/Zr 0.5 0.5 0.3533 0.0955 10 0.49 0.3531
0.0944 9.9955 1.73 clear Arg/Zr 1 1 0.3533 0.1910 10 1.00 0.3534
0.1912 10.0117 2.59 clear Arg/Zr 2 2 0.3533 0.3819 10 2.00 0.3540
0.3818 10.0140 gel Arg/Zr 3 3 0.3533 0.5729 10 2.99 0.3541 0.5729
9.9993 gel Arg/Zr 4 4 0.3533 0.7638 10 4.01 0.3526 0.7639 9.9970
gel
[0080] SEC-RI analysis was carried out on the sample with Arg/Zr
molar ratio of 1. SEC was equipped with a differential refractive
index (dRI) detector. Separation was carried out using a Protein
Pak 125 column by Waters (Milford, Mass.) with 20 min run time and
1 mL/min flow rate. The mobile phase consisted of deionized water
acidified with 1.01% w/w HNO.sub.3 to pH 2.3. SEC chromatogram
exhibited a peak at 6.75 minute (FIG. 1). A peak in this region of
retention time is commonly present in various non-activated
antiperspirant active salts, but seldom observed in aluminum-free
zirconium compounds. Based on the SEC data, it was predicted that
the prepared zirconium compound is a zirconium-based cluster
(zirconium oxychloride cluster) with a particle size of the order
of nanometer. Synchrotron-small-angle X-ray scattering (SAXS)
analysis was further carried out to determine the radius of
gyration of the zirconium oxychloride cluster. The distribution of
radius of gyration was extracted from the SAXS data using Guinier
plot analysis. There existed a main peak near 1.1 nm and a small
shoulder peak near 2 nm. The SAXS analysis showed that radius of
gyration of most zirconium oxychloride clusters is within 0.8 nm-3
nm.
Example 2: Purification of Zirconium Oxychloride Clusters
[0081] A 100 g batch was prepared according to Table 2. 1% w/w
zirconium oxychloride (ZrOCl.sub.2.8H.sub.2O, MW 322.25) and
arginine were mixed in aqueous solution with the molar ratio of
arginine to zirconium oxychloride of 1:1.
TABLE-US-00002 TABLE 2 1% zirconium oxy chloride with arginine (1:1
ratio) (100 g batch) Calculated Experimental Arg/ To- Arg/ To- Sam-
Zr Zr Arg tal Zr Zr Arg tal ple mol g g g mol g g g pH Arg/ 1
3.5325 1.9096 100 1 3.53 1.91 100.06 2.31 Zr 1
[0082] The zirconium oxychloride cluster was prepared as described
in Example 1. The prepared zirconium oxychloride cluster was
purified by gel permeability chromatograph (GPC). GPC column was
prepared using Bio-Rad P2 gel with 5 .mu.m particle size.
Approximately 10 mL of prepared solution was filtered (0.45 .mu.m)
and loaded on the column using a HPLC pump at 0.2 mL/min. The
mobile phase of the GPC chromatography was deionized water. Elution
fractions were collected in intervals and monitored using SEC-RI.
The first species to elute exhibited a peak of SEC at 6.75 minute
indicative of the zirconium oxychloride clusters. Highest
concentration of the zirconium oxychloride clusters was observed in
the 1160-1300 min GPC fraction. SEC-RI chromatogram of GPC fraction
1160-1300 min is shown in FIG. 2. The pH of the GPC fraction
(1160-1300 min) was 4.5. The zirconium oxychloride cluster in this
GPC fraction was stable in terms of gelation and flocculation. 10 g
of this fraction was freeze dried to obtain purified powder for
subsequent PXRD analysis. PXRD (Powder X-Ray Diffraction) analysis
revealed non-crystalline packing arrangements, indicating the
zirconium oxychloride cluster is amorphous.
Example 3: Flocculation
[0083] One of mechanisms of antiperspirant action is that
antiperspirants combine with proteins present in the sweat to form
a precipitate which blocks the sweat glands. To test whether the
zirconium oxychloride cluster, also referred to as Zr Peak 1
herein, can precipitate in a sweat environment and thus behave as
an antiperspirant, bovine serum albumin (BSA) was used as a model
protein to simulate proteins found on skin surface and sweat
environments. Zirconium oxychloride cluster was prepared as
described in Example 1. Specifically, 94.6 g of water was added to
3.5377 g of zirconium oxychloride (ZrOCl.sub.2.8H.sub.2O) in a
glass jar to yield a clear solution. Under stirring, 1.9104 g of
L-arginine was slowly added to prevent clumping of arginine as well
as large fluctuations in localized pH values. This clear solution
was heated at 50.degree. C. for 24 hours. Then the solution was
cooled to room temperature. After preparation of the Zr Peak 1
solution, 1% w/w solution of BSA was freshly prepared and sonicated
until the solution becomes clear. 1% BSA solution was subsequently
added dropwise to the Zr Peak 1 solution, at which point
precipitation was observed. This result shows that the zirconium
oxychloride cluster (Zr Peak 1) can form a precipitate in presence
of proteins such as BSA, suggesting that the zirconium oxychloride
cluster can flocculate proteins present in the sweat to enhance the
formation of plugs in the sweat ducts. This result suggests that
the zirconium oxychloride cluster can be used as an antiperspirant
and deodorant active.
[0084] While the disclosure has been described with respect to
specific examples including presently preferred modes of carrying
out the disclosure, those skilled in the art will appreciate that
there are numerous variations and permutations of the above
described systems and techniques. It is to be understood that other
embodiments may be utilized and structural and functional
modifications may be made without departing from the scope of the
present disclosure. Thus, the scope of the disclosure should be
construed broadly as set forth in the appended claims.
* * * * *